IL27374A - Preparation of organic boron derivatives - Google Patents

Preparation of organic boron derivatives

Info

Publication number
IL27374A
IL27374A IL27374A IL2737467A IL27374A IL 27374 A IL27374 A IL 27374A IL 27374 A IL27374 A IL 27374A IL 2737467 A IL2737467 A IL 2737467A IL 27374 A IL27374 A IL 27374A
Authority
IL
Israel
Prior art keywords
boron
general formula
preparation
organic
ether
Prior art date
Application number
IL27374A
Original Assignee
Montedison Spa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Montedison Spa filed Critical Montedison Spa
Publication of IL27374A publication Critical patent/IL27374A/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02Boron compounds
    • C07F5/027Organoboranes and organoborohydrides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Description

preparation of organic boron derivatives This invention relates to the preparation of organic boron derivatives having direct bonds between carbon and boron and the general formula in which represents an alkyl cycloalkyl or aralkyl Organic boron compounds of the type can be prepared by reactin a suitable reagent of the in which is as defined above and X represents a halogen atom such as a bromine or iodine with a boron compound such as a boron halide or an alkyl or with the reaction product of either of these with In this the reagent must first be prepared by a separate and then it is reacted with the boron This operating procedure has the considerable drawbacks and disadvantages that it requires a very long reactio and in the separate preparatio of the reagent it is essential to use large quantities of it is necessary to adopt stringent precautionary measures because of the presence of the highly inflammable Also this tion requires the use of expensive boron some of which could not readily be available on the The has been made with a view to overcoming or reducing these drawbacks and According to the invention there is provided a process for the preparation of organic boron compounds having direct boro carbon bonds and the general in which R represents an cycloalkyl or aralkyl grou comprising reacting a compound having the general RX in which represents an group with a linear or branched chain and containing from 2 to 6 carbon or a phenyl or a substituted phenyl and n is 1 or with a suspension of magnesium in an inert organic hydrocarbon solvent in the sence of a catalytic amount of According to a preferred embodiment of the the compound having the general formula in which R is as above and X represents a halogen atom such as a bromine or iodine radical and a boron derivative are at a temperature of from 80 to with a suspension of magnesium in an organic hydrocarbon solvent in the presence of a catalytic amount of an These processes in accordance with the invention have the advantages that they are effected in a single reaction stage and also the boron derivatives used are relatively cheap and easy to There is a wide range of arylalkyl and cycloalkyl halides which can be used as the compound represented by the formula Preferred compounds for the halogenated derivatives of aliphatic hydrocarbons with a straight or branched chain containing from 2 to 6 carbon the hexyl halides and the aryl and arylalkyl halogenated derivatives such as chlorobenzene benzylchloride and As a modification of the a mixture of two or more compounds represented by RX can be used and then the organic boron compound may have at least one group represented by R different from the other groups represented by The boron derivative is one having the general A in which represents an radical having a straight or branched chain and from 2 to 6 carbon atoms or a pheny or substituted phenyl and n is 1 or but is preferably less than Such derivatives can be prepared from an alcohol or phenol and orthoboric acid according to the method described Israel in our Application According to the method described in that application the organic boron derivatives with the above which are generally known as polyborates or are prepared by reacting an alcohol or a phenol with partially dehydrated boric the dehydration of the acid and its subsequent tion in the same apparatus being effected in an inert organic liquid The boron derivative is obtained in the form of a solu tion or suspension in the inert organic liquid medium when this inert organic liquid is a his solution or pension can be advantageously used at the source of boron in the process according to the present When compared with the previously used boron compounds such as the boron the esters of boric acid and the reaction products of these latter with boric anhydrides the compounds of the prepared as above have the advantage that they far less expensive and are easily prepared in high yields from boron compounds such as which is readily obtainable at prices far lower than the prices of boron halides of the boric simply adding the metal to an inert hydrocarbon solvent presence of a catalytic amount of an Suitable inert organic solvents which be used for all those which do not boil under the reaction temperature which is normally higher than and is preferably from 80 to By way of illustration preferred solvents are ethylbenzene ethylpropylbenzene propylbenzene and or Particularly suitable solvents are those inert organic liquids that may act as solvents or as suspending agents for the boron compounds having the formula such as for instance diethylbenzene and The magnesium metal is but not activated with very small quantities of ethyl before In the process according to the invention ether is used in very small It has been surprisingly and this constitutes an important advantage of this that traces of ether are quite sufficient to promote the formation of organic boron compounds having the formula in industrially acceptable Good results are obtained with an ether in such an amount that the ratio of ether to compound having the formula is from to The ether which can be used may be selected from a wide Particularly suitable proved to be diethyl ether and di n but l In the process according to this invention the ratios between the various compounds by lead to the organic boron compound having the and having direct links may vary within very wide According to a preferred form of the magnesi metal ether in catalytic quantities and an organi hydrocarbon liquid instance are placed in a After heating to a temperature of about the type compound and a boron type compound are added in the form of a solution or a suspension in an organic inert hydrocarbon but not the same as used for the preparation of the magnesium By properly regulating the the temperature of the reaction mixture can be maintained between 80 and Then after reaction the organic boron derivative can be obtained from the reaction mixture by The invention will now be illustrated by following t g of magnesium shavings were placed in a 4 1 fitted with a a a gas inlet pipe and a dipped dripping The reactor was flushed with a niirogen and then g of diethyl 5 ml of ethyl iodide and ml of diethylbenzene mixture of the three were introduced through the The mixture was stirred and heated to upon a mixture of 290 g of ethyl chloride and 450 ml of a solution in diethylbenzene of ethyl polyborate slowly dripped into the Because of the reaction of the two the temperature of the reaction mixture tended Therefore the rate of addition was regulated so as to keep the temperature around Once the mixing of the reactants had been complete the reaction mass was kept for a further 1 hour at the of The reaction mixture was then distilled under nitrogen current and the fraction boiling at was g of were the yield being calculated with respect to the starting EXAMPLE 2 Using a reactor similar to the one described in Example a suspension of 108 g of magnesium in 1200 ml of diethylbenzene was made in the Also of ether and 5 ml of ethyl iodide were After the suspension had been heated to a temperature of a mixture 490 g of and 450 ml of a solution of ethyl similar to that of the preceding was slowly dripped into the mixture with The addition was effected in such a way as to keep the temperature of the reaction mass between 100 and 1 Once all the reactants had been the reaction mixture was kept for a further hour at a temperature of Then the mixture was distilled under a slow nitrogen current and the fraction boiling at was The yield of was calculated with respect to the starting EXAMPLE 5 dripping 21 kg of raw crystalline magnesium 250 litres of diethylbenzene and 20 litres of diethyl ether were This mixture was then heated with stirring to a temperature of at a rate of 50 to 60 a mixture of 681 of ethyl chloride and 1 of a solution in diethylbenzene of ethyl polyborate having a boron content of was fed into the The addition of the mixture was effected at such a rate as tomaintaln the temperature at between 90 and After the addition of the the reaction mixture was then Kept for another hour at a temperature of from 90 to The reaction mixture was then distilled under a light nitrogen current and the fraction boiling at 94 to 96o G was Kg of were corresponding to a with respect to the starting of EXAMPLE 4 Into a 1000 ml similar to the one described in Example a mixture of 18 g of magnesium shavings g of diethyl ether 1 ml of ethyl iodide and 200 ml of diethylbenzene was The mixture was heated with stirring to and then a mixture of 118 g of and g of a solution in diethylbenzene of ethyl polyborate a boron content of by weight and a ratio of B to of was slowly dripped into the was obtained in a yield of 68 with respect to the starting EXAMPLE 5 Following the operational procedure of Example 4 and using the same 1 ml of ethyl g of diethyl a mixture of g of and g of a ratio of B to of were dripped into a suspension of 18 g of magnesium in 200 ml of Keeping the reaction temperature at about butylboron was obtained in a yield of with respect to the starting 6 Following the operation procedure of Example 4 and using the same a mixture of 89 g of chlorocyclohexane and ml of a solution in diethylbenzene of ethyl polyborate ratio equa to was reacted with a suspension of 18 g of magnesium in 200 ml of g of diethyl ether and 1 ml of ethyl The temperature was maintained at about during the Borotricyclohexane was formed with a yield of with respect to the starting EXAMPLE 7 Following the operational procedure and using the same reactants as in Example except that g of benzyl bromide instead of chlorocyclohexane was the action was The reaction was effected at a temperature of between 160 and The yield of was with respect to the 8 By operating as in the preceding g of magnesium in a suspension of 1200 ml of diethylbenzene which also contained 7 g diethyl ether and 5 ml of ethyl were reacted with 490 g of ethylbromide and 450 ml of a solution of ethyl polyborate similar to that of Example at a temperature of Triethyl boron was formed with a yield calculated on the starting boron of EXAMPLE 9 Following the procedure of the preceding Examples 18 g of magnesium suspended in 200 of diethylbenzene and which also contained g of diethylether and 1 ml of were reacted with 82 g of ethylbromide and a solution in diethylbenzene of butylpolyborate having a titre in boron of by weight and a ratio of B to of The reaction temperature was kept between 100 and was obtained with a yield of calculated with respect to the starting EXAMPLE Following the procedure of the preceding 18 g of magnesium suspended in 200 ml of diethylbenzene which al30 contained g of diethylether and 1 ml of were reacted with 82 g of ethylbromide and a solution in benzene of phenyl polyborate a titre in boron of and a ratio of B to of The reactio temperature was between 100 and Triethylboron was obtained in a yield of with EXAMPLE Example 10 was repeated using instead as the boron derivative ethoxy boroxine form of a solution of 18 g of boron compound in 100 ml of The reaction temperature was kept between 100 and Triethylboron was obtained in a yield of with respect to the starting 12 insufficientOCRQuality

Claims (9)

1. A process for the preparation of organic boron compounds having direct boron-carbon bonds and the general formula: BR, 3 in which R represents an alkyl, aryl, cycloalkyl or aralkyl group, comprising reacting a compound having the general formula: RX in which R is as above and X represents a chlorine, bromine or iodine atom, and a boron derivative having the general formula: ( '0)3B.(B203)n in which R* represents an alkyl group with a linear or branched chain and containing from 2 to 6 carbon atoms, or a phenyl or a substituted phenyl group, and n is 1 or larger, with a suspension of magnesium in an inert organic hydrocarbon solvent in the presence of a catalytic amount of an ether.
2. A process as claimed in Claim 1 in which the reaction is effected in the presence of an ether in such an amount that the molar ratio of ether to the compound having the formula RX is from 0.01 to 0.5.
3. A process as claimed in Claim 1 or 2 which is effected at a temperature of from 80 to 180°C.
4. A process as claimed in any preceding Claim in which a small quantity of ethyl iodide is added to the suspension of magnesium before the reaction.
5. A process as claimed in any preceding Claim in which n is less than 2.
6. A process as claimed in any preceding Claim in which - 13 - 27374/2 in Claim 1 of British Patent Serial No. 1156980.
7. A modification of the process claimed in any preceding claim for the preparation of organic boron compounds having direct boron-carbon bonds and the general formula BH^, in which at least one group represented by R is different from the other groups represented by R, comprising using a mixture of two or more different compounds having the general formula RX.
8. A process according to Claim 1 for the preparation of organic boron compounds having direct boron-carbon bonds and the general formula BR-jf substantially as herein described with reference to any Example.
9. An organic boron compound when prepared by a process as claimed in any preceding claim. mz
IL27374A 1966-02-03 1967-02-01 Preparation of organic boron derivatives IL27374A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT229666 1966-02-03
IT1409166 1966-02-03

Publications (1)

Publication Number Publication Date
IL27374A true IL27374A (en) 1970-11-30

Family

ID=26325233

Family Applications (1)

Application Number Title Priority Date Filing Date
IL27374A IL27374A (en) 1966-02-03 1967-02-01 Preparation of organic boron derivatives

Country Status (10)

Country Link
US (2) US3502729A (en)
BE (1) BE693650A (en)
CH (1) CH477477A (en)
DE (1) DE1618645A1 (en)
ES (1) ES336839A1 (en)
FR (1) FR1517893A (en)
GB (1) GB1169603A (en)
IL (1) IL27374A (en)
NL (1) NL6701488A (en)
SE (1) SE331995B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232224B (en) * 2018-10-26 2021-02-19 西安凯立新材料股份有限公司 Preparation method of 2-phenylpropionic acid

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2880243A (en) * 1956-05-09 1959-03-31 Olin Mathieson Manufacture of trisubstituted boranes
US3090801A (en) * 1956-07-06 1963-05-21 American Potash & Chem Corp Aryl polyboronic acids and esters and process for their preparation
US2939885A (en) * 1957-07-29 1960-06-07 Olin Mathieson Production of trialkylboranes
US2862952A (en) * 1957-08-26 1958-12-02 American Cyanamid Co Method of preparing b-hydrocarbonsubstituted boron compounds
US3345418A (en) * 1957-08-29 1967-10-03 Herbert C Brown Catalytic process for preparing organoboron compounds from diborane
US3100181A (en) * 1961-02-16 1963-08-06 Nalco Chemical Co Preparation of organoboranes
US3405179A (en) * 1963-11-08 1968-10-08 M & T Chemicals Inc Method of preparing arylborane compounds
NL6415119A (en) * 1964-01-02 1965-07-05

Also Published As

Publication number Publication date
ES336839A1 (en) 1968-02-16
BE693650A (en) 1967-08-03
DE1618645A1 (en) 1971-04-01
GB1169603A (en) 1969-11-05
US3594426A (en) 1971-07-20
US3502729A (en) 1970-03-24
SE331995B (en) 1971-01-25
FR1517893A (en) 1968-03-22
NL6701488A (en) 1967-08-04
CH477477A (en) 1969-08-31

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